Esters for polyhalogen compounds of alcohols with therapeutically-active acids.



'tion the esterificatio-n of alcohols containing petroleum spirit (ligroin) dissolve in the RICHARD WOLFFENS'I'EIN, OF BERLIN, GERMANY.

ESTERS 0F POLYHALOGEN COMPOUNDS OF ALCOHOL-S WITH THERAPEUTICALLY- ACTIVE ACIDS.

N-o Drawing.

Specification of Letters Patent.

Patented Sept. 2, 191 3.

Application filed March 1. 1913. Serial No. 751,642.

T 0 all whom 1'15 may concern Be it known that l, R-ionauo WoLrrnN- STEIN, professor of chemistry, a subject of the German Emperor, residing at Berlin, Germany, have invented new and useful Improvements Relating, to Esters of Polyhalogen C()II1I)Olll1(.lS of Alcohols with Therapeutically-Active Acids, of which the following is a specification.

lolyhalogen compounds otalcohols which by themselves generally have a strong anesthetic etlect, have already been combined with acetyl-salicylic acid, important for therapeutic purposes; so as to form the corres 'mnding esters. This manufacture is, however, troublesome, because the reaction must be carried out in the presence ot substances adapted to combine with the hydro chloric acid which is liberated in the process.

I have found, that contrary to cxpectapolyhalogens with acids having tl'ierapcutic properties, into whose phenol group no acid groups have entered, is substantially simpler and may be etl'eeted by merely heating the compounds. A very simple method consists, for instance, in combining salicylic acid as such with the alcohols or in producing the corresponding combination with cresotinic acid other. For instance 95 grams of salicylic acid chlorid are heated with 101 grams of tertiary trichloro-lnityl alcohol for about 11} hours at 120 to 140 C. The salicylate of trichloro-biltyl-alcohol thus formed, will on treatment of the mac tion product with dilute soda solution and latter and may be separated by crystallization. The compound crystallizes well and melts at about 8l-82 0., it boils at 170 C. with slight decomposition, it is easily soluble in alcohol, soluble also in ether and petroleum spirit, but sparingly soluble in water. WVhcn treated with chlorid of iron, the solution of the ester in dilute alcohol assumes a violet color with a slightly reddish tint. When treated with concentrated sulfuric acid, the ester at first dissolves in it,

chlorid. Both ol these methods yield good results. Salicylic acid chlorid at ordinary temperature is a colorless oil which boils at about 92 (J. under a pressure of fifteen millimeters and on cooling solidifies to crystals, which melt again at about 12 C.

It is not necessary to start from readylormed salicylic chlorid, but in order to produce the trichlorobutylsalicylic ester, (33 grams of salicylic'acid may be heated with 75 grams of tertiary trichloro butyl alcohol amt-:30 grams of zinc chlorid for about 2 hours to a temperature between 100 and The separation or isolation of the compound takcs place in the manner described above.

The combination of the paracresotinic acid with acetonechloroform yields acetonechloroform paracresotinic ester, which crystallizes well and melts at 97 C.

Tn the polyhalogen compounds of alcohols to be employed the halogen atoms are preferabl y arranged on one carbon atom.

The above compounds are intended for therapeutic purposes.

What I claim is:-

, 1. The recess for the manufacture of salicylic trichloro-butyl-ester, which consists in heating salicylic acid chlorid with tertiary trichloro-butyl-alcohol, treating the product of the reaction with dilute soda solution and petroleum spirit, and allowing it to crystallize from the solution thus formed, substantially as described.

2. As a new product, salicylic trichlorobutyl-ester, being an easily crystallizable compound melting at 81-82 (1, boiling at giving off abundant vapors of hydrochloric 10 170 (J. With slight decomposition, easily acid. I

soluble in alcohol, soluble also in ether and In testimony whereof I aflix my signature petroleum spirit, but sparingly soluble in in presence of two Witnesses.

5 Water assumin a Violet color with slightly 1 T reddish tint, Wl ien treated in alcoholic solu- RICHARD WOLFFENSTEII\' tion with chlorid 01": iron, soluble in c0ncen Witnesses: tratcd sulfuric acid and when heated in this HENRY HASPER,

solution, undergoing decomposition While W'QLDEMAR HAUPT. 

